溶液法合成端羧基聚丁二烯

以过氧化戊二酸为引发剂，无水乙醇或丙酮为溶剂，采用自由基型溶液法合成了端羧基聚丁二烯，并用ＩＲ对聚合物的微观结构进行了表征。结果表明当聚合反应温度为１０５￣１１５℃时，合理搭配引发剂起始用量和连续加入引发剂的递减速率，可合成满足不同应用领域的端羧基聚丁二烯产品。     

Effects of Genetically Engineered Stem Cells Expressing Cytosine Deaminase and Interferon-Beta or Carboxyl Esterase on the Growth of LNCaP Prostate Cancer Cells

The risk of prostate cancer has been increasing in men by degrees. To develop a new prostate cancer therapy, we used a stem cell-derived gene directed prodrug enzyme system using human neural stem cells (hNSCs) that have a tumor-tropic effect. These hNSCs were transduced with the therapeutic genes for bacterial cytosine deaminase (CD), alone or in combination with the one encoding human interferon-beta (IFN-β) or rabbit carboxyl esterase (CE) to generate HB1.F3.CD, HB1.F3.CD.IFN-β, and HB1.F3.CE cells, respectively. CD enzyme can convert the prodrug 5-fluorocytosine (5-FC) into the activated form 5-fluorouracil (5-FU). In addition, CE enzyme can convert the prodrug CPT-11 into a toxic agent, SN-38. In our study, the human stem cells were found to migrate toward LNCaP human prostate cancer cells rather than primary cells. This phenomenon may be due to interactions between chemoattractant ligands and receptors, such as VEGF/VEGFR2 and SCF/c-Kit, expressed as cancer and stem cells, respectively. The HB1.F3.CE, HB.F3.CD, or HB1.F3.CD.IFN-β cells significantly reduced the LNCaP cell viability in the presence of the prodrugs 5-FC or CPT-11. These results indicate that stem cells expressing therapeutic genes can be used to develop a new strategy for selectively treating human prostate cancer.     

The preparation of α‐bis and α,ω‐tetrakis aromatic oxazolyl‐ and carboxyl‐functionalized polymers using 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

The preparation of new compounds, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethanol and a new symmetrically disubstituted 1,1‐diphenylethylene derivative, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene, is described. 1,1‐Bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene was utilized as a dioxazolyl initiator precursor for the polymerization of styrene by atom transfer radical polymerization (ATRP) methods to produce α‐bis(oxazolyl) polystyrene. The kinetic study of the polymerization process indicated that the free radical polymerization reaction for the preparation of α‐bis(oxazolyl) polystyrene follows first‐order rate kinetics with respect to monomer consumption. α,ω‐Tetrakis(oxazolyl) polystyrene was prepared by a new, in situ, controlled/living, post‐ATRP chain‐end‐functionalization reaction which involves the direct addition of 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene to the ω‐terminus of the α‐bis(oxazolyl) polystyrene derivative, without the isolation and purification of the polymeric precursor. α‐Bis(carboxyl) and α,ω‐tetrakis(carboxyl) polystyrene derivatives were obtained by the quantitative chemical transformation of the oxazoline groups of the respective aromatic oxazolyl chain‐end‐functionalized polystyrene derivatives to the aromatic carboxyl groups. The organic precursor compounds, the dioxazolyl‐functionalized 1,1‐diphenylethylene derivative and the functionalized polymers were characterized using ¹H NMR and ¹³C NMR spectrometry and Fourier transform infrared spectroscopy, size‐exclusion and thin‐layer chromatography and non‐aqueous titration measurements. © 2014 Society of Chemical Industry     

Novel Redox-Dependent Esterase Activity (EC 3.1.1.2) for DJ-1: Implications for Parkinson’s Disease

Mutations the in human DJ-1 (hDJ-1) gene are associated with early-onset autosomal recessive forms of Parkinson’s disease (PD). hDJ-1/parkinsonism associated deglycase (PARK7) is a cytoprotective multi-functional protein that contains a conserved cysteine-protease domain. Given that cysteine-proteases can act on both amide and ester substrates, we surmised that hDJ-1 possessed cysteine-mediated esterase activity. To test this hypothesis, hDJ-1 was overexpressed, purified and tested for activity towards 4-nitrophenyl acetate (pNPA) as µmol of pNPA hydrolyzed/min/mg·protein (U/mg protein). hDJ-1 showed maximum reaction velocity esterase activity (V_max = 235.10 ± 12.00 U/mg protein), with a sigmoidal fit (S_0.5 = 0.55 ± 0.040 mM) and apparent positive cooperativity (Hill coefficient of 2.05 ± 0.28). A PD-associated mutant of DJ-1 (M26I) lacked activity. Unlike its protease activity which is inactivated by reactive oxygen species (ROS), esterase activity of hDJ-1 is enhanced upon exposure to low concentrations of hydrogen peroxide (<10 µM) and plateaus at elevated concentrations (>100 µM) suggesting that its activity is resistant to oxidative stress. Esterase activity of DJ-1 requires oxidation of catalytic cysteines, as chemically protecting cysteines blocked its activity whereas an oxido-mimetic mutant of DJ-1 (C106D) exhibited robust esterase activity. Molecular docking studies suggest that C106 and L126 within its catalytic site interact with esterase substrates. Overall, our data show that hDJ-1 contains intrinsic redox-sensitive esterase activity that is abolished in a PD-associated mutant form of the hDJ-1 protein.     

二元醇共价交联羧基化石墨烯复合膜和正丁醇脱水性能

以二元醇（乙二醇、1,3-丙二醇和1,4-丁二醇）为交联剂,通过抽滤的方式在涂覆盐酸多巴胺的聚醚砜（PES）支撑层上制备了共价交联的羧基化石墨烯/聚醚砜（CG/PES）复合膜。稳定性测试证明盐酸多巴胺的涂覆和二元醇的交联显著提高了分离层和支撑层以及CG纳米片间的结合力。采用扫描电子显微镜、X射线衍射仪、X射线光电子能谱仪和水接触角测试仪对复合膜的物化性质和微观形貌进行了表征。结果表明,所得复合膜的分离层连续无缺陷,厚度在60~64nm之间。二元醇与CG纳米片上的羧基成功发生反应,将CG纳米片锚固在一起。交联剂的引入没有大幅降低亲水性且实现了对分离层层间距的有效调控,随二元醇分子尺寸增加,所得复合膜的层间距由0.761nm提高到0.778nm。CG/PES复合膜对正丁醇/水混合物具有优良的渗透汽化分离性能。在料液温度为50℃、料液中水的质量分数为10%时,三种交联剂所得复合膜的渗透通量分别达到0.79kg/(m²·h)、0.87kg/(m²·h)和0.96kg/(m²·h),而分离因子比未交联的复合膜高一个数量级。15天的稳定性测试结果表明,所得复合膜分离性能无显著变化,能够满足渗透汽化应用要求。     

羧基改性聚乙烯醇的制备及水溶性研究

通过丙烯酸(AA)与乙酸乙烯酯(VAc)共聚进而醇解的方法合成出具有高醇解度、低结晶度的丙烯1酸改性聚乙烯醇。通过FT-IR和H-NMR对聚合物的化学结构进行了表征;通过XRD、UV-Vis、剪切流变测试等手段研究了丙烯酸结构单元含量对改性PVA的结晶性能、水溶性能和溶液表观黏度的影响。结果显示,通过引入适量丙烯酸结构单元,可降低PVA结晶度,提高PVA水溶性,增强PVA水溶液表观黏度的剪切稳定性。     

羧基配位剂对电镀镍–磷合金的影响

以羧基类物质作配位剂,在A3钢板表面电沉积制备Ni–P合金镀层。镀液基础组成和工艺参数为:NiSO4·6H2O 240 g/L,NiCl2·6H2O 45 g/L,NaH2PO2·H2O 50 g/L,H3BO3 35 g/L,NaF30 g/L,pH 2.0,温度70°C,电流密度2.5 A/dm2,时间20 min。研究了镀液中羧基配位剂含量对Ni–P镀层沉积速率和耐蚀性的影响。结果表明,随羧基配位剂含量增大,沉积速率减小,镀层耐蚀性先改善后变差。其适宜含量为20~30 g/L。羧基配位剂含量为25 g/L时,镀层外观光亮、结合力良好,耐蚀性和耐磨性优于未加配位剂的镀层。镀层的P含量为18.11%,属于高磷非晶态Ni–P镀层。羧基配位剂具有细化镀层晶粒的作用,使镀层表面更为平整、致密。     

羧酸膦酸型化合物的阻垢缓蚀性能的量子化学研究

运用密度泛函(DFT)理论,在B3LYP／6—31G*水平下,系统研究了2-膦酸基丁烷-1,2,4-三羧酸(PBTCA)、1,2,2-三膦酸基丁烷-4-羧酸(TPBCA)、3,3-二膦酸基戊烷-1,5-二羧酸(DPPDCA)这3种羧酸膦酸型阻垢缓蚀剂的分子结构与阻垢缓蚀性能之间的构效关系。结果表明,3种膦酸分子中的羧基和膦酸基中氧原子的负电荷较多,氧原子与垢晶体中的钙离子产生静电,这些氧原子对间距与方解石晶体生长面上的钙离子对间距匹配,产生晶格畸变,阻止垢体生长。计算得到3种分子的缓蚀能力为PBTCA>DPPDCA>TPBCA,并且得到羧基中的O原子、膦酸基中的O原子对缓蚀能力贡献较大。     

Effect of amidation on the foaming and physico-chemical properties of bovine serum albumin

Amidation of bovine serum albumin (BSA) was achieved by a water-soluble carbo-diimide, ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)-mediated reaction using ammonium chloride as the nucleophile. Partial and substantial amidation of 0.5% (w/v) BSA in 5.5 m ammonium chloride solution with 1 times 10-²mmol EDC over 120 min and 1 times 10^-1mmol EDC over 10 min respectively was achieved on a large scale using diafiltration for rapid termination of the reaction and purification. Residual ammonium chloride otherwise enhanced foaming properties. The amidated proteins were characterized by isoelectric focusing, electrophoresis and hydrophobicity and disulphide- and sulphydryl-group measurements. Compared with native BSA, partially amidated BSA (PA-BSA) produced enhanced foam expansion and foam stability values. This was attributed to minimal denaturation and to the presence of both acidic and basic components (pI range 5.25–7.50) within the single protein. In contrast, substantially amidated BSA (SA-BSA) (pI range 7–9.1) had similar foaming properties to those of the ultrafiltered BSA control which were slightly lower than those of native BSA. However SA-BSA interacted synergistically with native BSA producing enhanced foaming properties particularly at the 1:1 ratio through electrostatic interactions, conformational changes and increased hydrophobicity.     

共聚PET固相聚合粘度变化规律的研究

利用固相聚合生产装置,研究了共聚PET固相聚合反应温度、停留时间、氮气流量、催化剂含量、基础切片端羧基含量对增粘的影响。结果表明:在一定的工艺条件下,产品粘度随反应温度提高、停留时间的延长及催化剂含量的增大而增大;当气固比大于0.3时,增大氮气流量对增粘速率不再产生影响。